Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/32—Oxygen atoms
  • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
  • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
  • A01N41/10—Sulfones; Sulfoxides
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
  • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
  • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
  • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
  • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
  • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
  • A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
  • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D309/10—Oxygen atoms
  • C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
  • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
  • C07D317/22—Radicals substituted by singly bound oxygen or sulfur atoms etherified
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/08—Esters of oxyacids of phosphorus
  • C07F9/09—Esters of phosphoric acids
  • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds

Definitions

• the present invention relates to diphenyl sulfone compounds, and'their production and use. More particularly, it relates to novel diphenyl sulfone compounds represented by the formula: wherein R 1 and R 2 are the same or different, each being a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, a phenoxy group, a lower alkylthio group, a lower alkylsulfonyl group or a lower alkoxycarbonyl(lower)alkoxy group, R 3 is a hydroxyl group, a lower alkenyloxy group, a lower alkynyloxy group, a halo (lower) alkoxy group, a dihalo(lower)-alkoxy group, a lower alkoxy(lower)alkoxy group, a cyano-(lower)alkoxy group,
• halogen may include chlorine, bromine, fluorine and iodine.
• Preferred diphenyl sulfone compounds are those of the formula (I) wherein R 1 and R 2 are the same ordifferent, each being hydrogen, fluorine, chlorine, bromine, C 1 -C 2 alkyl, C 1 -C 2 alkoxy, propenyloxy, propynyloxy, phenoxy, methylthio, methylsulfonyl or C 1 -C 2 alkoxycarbonyl(C 1 -C 2 )alkoxy, R 3 is hydroxyl, propenyloxy, propynyloxy, chloroethoxy, difluoromethoxy, C l -C 2 alkoxy-(C 1 -C 2 )alkoxy, cyanomethoxy, cyanomethoxymethoxy, hydroxyethoxy, ethoxycarbonyl, C 1 -C 2 alkylthio(C 1 -C 2 )alkoxy, ethenyloxyethoxy, N,N-di(C 1 -
• R l and R 2 are, same or different, each hydrogen, methyl, ethyl, fluorine, chlorine, bromine, methoxy or ethoxy
• R 3 is chloroethoxy, methoxymethoxy, cyanomethoxy, methoxycyanomethoxy, hydroxyethoxy, methylcarbonylmethoxy, a-(methylcarbonyl)ethoxy, methylthiomethoxy, methoxyiminopropoxy, diethoxyphosphinyloxy, oxotetrahydrofuranyloxy, methoxycarbonylmethoxy, ethoxy- carbonylmethoxy, a-(methoxycarbonyl)ethoxy, methoxy(methoxycarbonyl)methoxy, a-(ethoxycarbonyl)ethoxy, ethylthiocarbonylmethoxy, propinyloxycarbonylmethoxy, 2-methyl-1,3- oxo
• diphenyl sulfone compounds (I) are as follows: 4-(2-chloro-4-trifluoromethyl- phenoxy)-2-cyanomethoxy-4'-methyldiphenyl sulfone, 4-(2-chloro-4-trifluoromethylphenoxy)-2-cyanomethoxy-4'-chlorodiphenyl sulfone, 4-(2-chloro-4-trifluoromethylphenoxy)-2-methoxycarbonylmethoxydiphenyl sulfone, 4-(2-chloro-4-tri- fluoromethylphenoxy)-2-methoxycarbonylmethoxy-4'-methyldiphenyl sulfone, 4-(2-chloro-4-trifluoromethylphenoxy)-2-methoxycarbonylmethoxy-4'-chlorodiphenyl sulfone, 4-(2-chloro-4-trifluoromethylphenoxy)-2-methoxycarbonylmethoxy-4'-chlorodiphenyl s
• herbicides are required to be so effective as to exterminate many undesired weeds growing in paddy rice field, crop field, orchards, etc. Further, it is desirous that herbicides show a prominent while herbicidal activity against a wide variety of weeds/causing no or lesser damage to important crop plants.
• the use of herbicides in a large dose may occasionally produce a high preventive effect; however, this results in/increase of the in a phytotoxicity to crop plants and thus/decrease of the crop yield.
• the environmental pollution due to agricultural chemicals nowadays is a great social problem, and herbicides should therefore produce a significant herbicidal effect in a small dose and be less residual.
• the diphenyl sulfone compounds (I) show a strong herbicidal activity against a wide variety of weeds including broad-leaved weeds such as radish (Raphanus sativus), velvetleai (Abutilon theophrasti), sunflower (Helianthus annuus) , Cocklebur (Xanthium pennsylvanicum), tall morningglory (Ipomoea purpurea), hemp sesbania (Sesbania sp.), redroot pigweed (Amaranthus retroflexus), birdseye speedwell (Veronica persica), black nightshade (Solanum nigrum), prickly sida (Sida spinosa), pineappleweed ( M atricaria spp.) and wild buckwheat (Polygonum convolvulus) and Graminaceous weeds such as barnyardgrass (Echinochloa crus-galli) and wild buckwheat (Polygonum convolvulus)
• Graminaceous weeds such as barnyardgrass, broad-leaved weeds such as false pimpernel (Lindernia procumbens), toothcup (Rotala indica), waterwort (Elatine triandra), Vandelcia angustifolia and Dopatrium junceum, Cyperaceae weeds such as nutsedge (Cyperus difformis), hardstem bulrush (Scirpus juncoides) and slender spikerush (Eleocharis acicularis), monochoria (Monochoria vaginalis), arrowhead (Sagittaria pygmaea), etc. .in paddy rice field by pre-emergence or post-emergence treatment.
• Graminaceous weeds such as barnyardgrass, broad-leaved weeds such as false pimpernel (Lindernia procumbens), toothcup (Rotala indica), waterwort (Elatine triandra), Vandelcia angust
• the diphenyl sulfone compounds (I) do not display any substantial toxicity via-a-vis inportant crop plants such as corn, wheat, soybean, cotton and rice plant. They show high herbicidal activity when applied to crop fields inpost-emergence foliar treatment, although herbicidal activity can also be produced in by pre-emergence treatment. In case of post emergence foliar treatment, such broad-leaved weeds as radish, velvetleat, sunflower, cocklebur, tall morningglory, hemp sesbania, redroot pigweed, birdseye speedwell and black nightshade can be exterminated. Their herbicidal activity extend to the Graminaceous weeds such as barnyardgrass and wild oat as well.
• the diphenyl sulfone compounds (I) have a high selectivity, with respect to the important crop plants and the harmful weeds germinated in the field oi such crop plants so that it becomes possible to control the germination of weeds without affecting the crop plants.
• sunflower, cocklebur, tall morningglory, hemp sesbania, velvetleaf, redroot pigweed, etc. in the field of corn or soybean can be controlled by an appropriate choice of the dosage while corn or soybean remain unaffected.
• radish, birdseye speedwell, black nightshade, etc. in the field of wheat can be controlled without causing any toxicity to wheat.
• the diphenyl sulfone compounds (I) have a high herbicidal effect on broad-leaved weeds while showing selectivityvis-a-vis crop .
• plants such as soybean, cotton, wheat and corn.
• the germination of harmful weeds such as barnyardgrass, false pimpernel, toothcup, hardstem bulrush and arrowhead in the paddy rice field is effectively prevented.
• the diphenyl sulfone compounds (I) can be used as herbicides applicable to paddy field as well as agricultural plowed field. They are also useful as herbicides to be employed for orchard, non-agricultural field, forest, etc.
• the diphenyl sulfone compounds (I) can be produced by various procedures, typical examples of which are shown below:
• the diphenyl sulfone compounds of the formula: wherein R 5 and R 6 are the same or different, each a being hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a phenoxy group, a lower alkylthio group or a lower alkylsulfonyl group and X is as defined above can be produced by reacting a compound of the formula: wherein R 7 is a lower alkoxy group and R 5 , R 6 and X are each as defined above, with an ether linkage cleaving agent in an inert solvent.
• the ether linkage cleaving agent there may be used a Lewis acid (e.g. boron tribromide, boron triiodide, ferric chloride, zinc chloride), a mineral acid (e.g. hydrochloric acid, hydrobromic acid, hydroiodic acid), etc.
• a Lewis acid e.g. boron tribromide, boron triiodide, ferric chloride, zinc chloride
• a mineral acid e.g. hydrochloric acid, hydrobromic acid, hydroiodic acid
• the inert solvent are aromatic hydrocarbons (e.g. benzene, toluene, xylene), chlorinated hydrocarbons (e.g. chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene), formic acid, acetic acid, nitroethane, nitrobenzene, water, etc.
• R 8 is a lower alkenyl group, a lower alkynyl group, a halo(lower)alkyl group, a lower alkoxy(lower)alkyl group, a cyano(lower)alkyl group, a lower alkoxycyano(lower)alkyl group, a hydroxy(lower)alkyl group, a lower alkylcarbonyloxy(lower)alkyl group, a lower alkylthio(lower)alkyl group, a lower alkenyloxy(lower)alkyl group, a di (lower) alkylamino(lower)alkyl group, a hydroxyimino(lower)alkyl group, a lower alkoxyimino(lower)alkyl group, a lower alkylsulfonyl group, a lower alkoxycarbonyl group, a di(lower)alkoxy
• the inert solvent examples include benzene, toluene, xylene, dimethylformamide, dimethylsulfoxide, methanol, ethanol, acetone, methylethylketone, etc.
• the hydrogen halide-eliminating agent there may be exemplified pyridine, triethylamine, N,N-dimethylaniline, N,N-diethylaniline, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium ethoxide, etc.
• the halide and the hydrogen halide-eliminating agent may be employed respectively in an amount of 0.9 to 2 equivalents to the starting compound (Ia).
• the reaction is normally effected at a temperature of 0 to 150°C, preferably of 20 to 100°C.
• the diphenyl sulfone compounds of the formula: wherein R 9 is a lower alkenyl group, a lower alkynyl group or a lower alkoxycarbonyl(lower)alkyl group and X is as defined above can be produced from a compound of the formula: wherein R 7 and R7 1 are each a lower alkoxy group and X is as defined above by reacting the latter with an ether linkage cleaving agent in an inert solvent and reacting the resultant compound of the formula: wherein X is as defined above with a halide of the formula: wherein Z is a halogen atom and R 9 is as defined above in an inert solvent in the presence of a hydrogen halide-eliminating agent.
• the ether linkage cleaving agent a Lewis acid (e.g. boron tribromide, boron triiodide, ferric chloride, zinc chloride), a mineral acid (e.g. hydrochloric acid, hydrobromic acid, hydroiodic acid) or the like.
• a Lewis acid e.g. boron tribromide, boron triiodide, ferric chloride, zinc chloride
• a mineral acid e.g. hydrochloric acid, hydrobromic acid, hydroiodic acid
• the inert solvent are aromatic hydrocarbons (e.g. benzene, toluene, xylene), chlorinated hydrocarbons (e.g.
• the amount of the ether linkage cleaving agent may be normally from 1.8 to 20 equivalents to the starting compound (III).
• the reaction is normally effected at a temperature of -50 to 150°C, preferably of 0 to 120°C.
• the hydrogen halide-eliminating agent pyridine, triethylamine, N, N -dimethylaniline, N,N-diethylaniline, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium ethoxide, etc.
• the inert solvent are benzene, toluene, xylene, dimethylformamide, dimethylsulfoxide, methanol, ethanol, acetone, methyl ethyl ketone, etc.
• the halide and the hydrogen halide-eliminating agent may be respectively employed in an amount of 1.8 to 4 equivalents to the compound (IV).
• the reaction is usually carried out at a temperature of 0 to 150°C, preferably of 20 to 100°C.
• the diphenyl sulfone compounds of the formula: wherein R 10 is a lower alkyl group or a halo(lower)alkyl group and R 5 , R 6 and X are each as defined above can be produced by reacting the compound (Ia) with an acid halide of the formula: wherein Q is a halogen atom and R 10 is as defined above in an inert solvent in the presence of a hydrogen halide-eliminating agent.
• inert solvent examples include benzene, toluene, xylene, chloroform, dichloroethane, chlorobenzene, dichlorobenzene, diethyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, ethyl acetate, methyl acetate, butyl acetate, nitroethane, nitrobenzene, acetonitrile, isobutyronitrile, pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine, etc.
• the hydrogen halide-eliminating agent may for instance be pyridine, triethylamine, N,N-dimethylaniline, N,N-diethylaniline, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, etc.
• the acid halide is ordinarily used in an amount of 0.9 to 1.5 equivalents to the compound (Ia).
• the reaction is normally effected at a temperature of -20 to 100°C, preferably of 0 to 60°C.
• diphenyl sulfone compounds of the formula: wherein B is a lower alkylene group and R 5 , R 6 , R 10 and X are each as defined above can be produced by reacting a compound of the formula: wherein B, R 5 , R 6 and X are each as defined above with an acid halide of the formula: wherein R 10 and Q are each as defined above in an inert solvent in the presence of a hydrogen halide-eliminating agent.
• inert solvent examples include benzene, toluene, xylene, chloroform, dichloroethane, chlorobenzene, dichlorobenzene, diethyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, ethyl acetate, methyl acetate, butyl acetate, nitroethane, nitrobenzene, acetonitrile, isobutyronitrile, pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine, etc.
• the hydrogen halide-eliminating agent there may be exemplified pyridine, triethylamine, N,N-dimethylaniline, N,N-diethylaniline, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, etc.
• the acid halide is employed in an amount of 0.9 to 1.5 equivalents to the compound (V).
• the reaction may be performed at a temperature of -20 to 100°C, preferably of 0 to 60°C.
• the diphenyl sulfone compounds of the formula: wherein R 11 is a lower alkyl group and R 5 , R 6 and X are each as defined above can be produced by reacting a compound of the formula: wherein R 11 and X are each as defined above with a diazotiating agent and sulfur dioxide in the presence of a copper catalyst in an inert solvent and reacting the resulting compound of the formula: wherein E is a halogen atom and R 11 and X are each as defined above with a phenyl halide of the formula: wherein W is a halogen atom and R 5 and R 6 are each as defined above in the presence of magnesium in an inert solvent.
• the combination of a nitrite (e.g. sodium nitrite) and a mineral acid (e.g. hydrochloric acid) may be employed as the diazotiating agent. It is usually employed in an amount of 0.9 to 1.2 equivalents to the compound (VI).
• the copper catalyst are metallic copper, copper oxide, copper chloride, etc.
• the reaction is ordinarily carried out at a temperature of -5 to 10° C , preferably of 0 to 5°C, for the diazotiation and at a temperature of -5 to 50°C, preferably of 0 to 30°C for the sulfonylation.
• magnesium is normally employed in the form of powder, ribbons, flakes, etc. Its amount may be from 0.9 to 1.5 equivalents to the compound (VII).
• the inert solvent are diethyl ether, tetrahydrofuran, etc.
• the reaction proceeds usually at a temperature of -30 to 80°C, preferably of -20 to 30°C. If desired, any reaction aid such as dilithium tetrachlorocuprate may be present in the reaction system.
• the diphenyl sulfone compounds of the formula: wherein R 12 is a lower alkyl group, R 13 is a hydrogen atom or a lower alkyl group and R 5 , R 6 , B and X are each as defined above can be produced by reacting a compound of the formula: wherein R 5 , R 6' R12, B and X are each as defined above with an amine of the formula: wherein R 13 is as defined above in an inert solvent.
• the amine may be employed in free form or salt form.
• salt form such as a salt with a mineral acid (e.g. hydrochloric acid, hydrobromic acid, sulfuric acid)
• a base e.g. pyridine, triethylamine, N,N-diethylaniline, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium acetate, sodium methoxide, sodium ethoxide
• the amount of the amine may be from 0.9 to 1.5 equivalents to the compound (VIII).
• the amount of the base to be used together with the amine in salt form may be from 0.9 to 1.5 equivalents to the compound (VIII).
• inert solvent examples include benzene, toluene, xylene, chloroform, dichloroethane, chlorobenzene, dichlorobenzene, diethyl ether, dioxane, tetrahydrofuran, methanol, ethanol, isopropanol, cyclohexanol, methyl celosolve, nitrobenzene, pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine, etc.
• the reaction temperature is normally from 0 to 120°C, preferably from 30 to 80°C.
• the resulting mixture was dropwise added to a mixture of p-methylbenzenethiol (3.9 g), sodium hydroxide (3.5 g), water (20 ml) and copper powder (0.8 g) kept at 40°C, and the resultant mixture was heated to about 100°C for 1 hour.
• the reaction mixture was extracted with ether, and the extract was washed with 10 % sodium hydroxide solution, water, 5 % hydrochloric acid and water in this order and then concentrated.
• the resulting oily substance was purified by silica gel column chromatography to give 10 g of 4-(2-chloro-4-trifluoromethylphenoxy)-2-methoxy-4'-methyldiphenyl sulfide.
• the extract was first washed with 5 % sodium hydroxide solution and then with water, dried over anhydrous magnesium sulfate and concentrated to give an oily substance, which was purified by silica gel column chromatography and crystallized from ethanol. Recrystallization from ethanol gave 2.8 g of 4-(2-chloro-4-trifluoromethylphenoxy)-2-methoxy-4'-methyldiphenyl sulfone. M.P., 156.5 - 159.5°C.
• the diphenyl sulfone compounds (I) as herbicides may be formulated into any conventional composition form such as emulsifiable concentrates, wettable powders, suspensions, granules and dusts.
• concentration of the active ingredient in such composition form is usually within a range of 0.1 to 90 % by weight, preferably of 1 to 80 % by weight.
• a solid or liquid carrier or diluent may be used.
• the solid carrier or diluent there may be employed mineral powders (e.g. kaolin, bentonite, talc, diatomaceous earth, sericite, synthetic hydrated silicon dioxide).
• the liquid carrier or diluent there may be employed aromatic hydrocarbons (e.g. xylene, methylnaphthalene), ketones (e.g. cyclohexanone, isophorone), chlorobenzene, dimethylformamide, cellosolve, ethylene glycol, water, etc.
• a surface active agent used for emulsification, dispersion or spreading may be any of the non-ionic, anionic, cationic and amphoteric type of agents.
• the surface active agent include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene styrylaryl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, oxyethylene- oxypropylene polymers, alkyl sulfates, alkyl sulfonates, dialkyl sulfosuccinate, alkylaryl sulfonates and the like.
• lignin sulfonates, polyviyl alcohol, methylcellulose or the like may be used as an auxiliary agent.
• One part of Compound No. 16 1 part of synthetic hydrated silicon dioxide, 5 parts of ligninsulfonate and 93 parts of clay are well mixed while being powdered. The mixture is then kneaded with water, granulated and dried to obtain granules.
• Compound No. 10 Twenty parts of Compound No. 10 are mixed with 60 parts of an aqueous solution containing 3 % polyoxyethylene sorbitan monooleate and pulverized until the particle size of the active ingredient becomes less than 3 microns. Twenty parts of an aqueous solution containing 3 % of sodium alginate as a dispersing agent are incorporated therein to obtain a suspension.
• the dosage rate of the diphenyl sulfone compounds (I) may vary depending upon the application mode, crop plants or weeds, kind of composition, weather, etc. Generally, however, the dosage rate may be from 0.5 to 200 grams, preferably from 1 to 50 grams, of the active ingredient per are.
• the diphenyl sulfone compounds (I) of the invention may be used together with other herbicides to improve their activity as herbicides, and in some cases, a synergistic effect can be expected.
• other herbicides include, for instance, phenoxy series herbicides such as 2,4-dichlorophenoxyacetic acid (2,4-D), 2-methyl-4-chlorophenoxyacetic acid (MCPA), 2-methyl-4-chlorophenoxy- butyric acid (2,4-DB), 2-(2-methyl-4-chlorophenoxy)propionic acid (mecoprop), methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]-propionate (dichlohopmethyl), butyl 2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]propionate (fluadihopbutyl) and 2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]propionic acid (including their esters
• the diphenyl sulfone compounds (I) may be applied in combination with insecticides, nemato- cides, fungicides, plant growth regulators, fertilizers, etc.
• diphenyl sulfone compounds (I) as herbicides will be illustrated in the following Examples wherein the phytotoxicity to crop plants and the herbicidal activity on weeds were evaluated as follows: the aerial parts of the test plants were cut off and weighed (fresh weight); the percentage of the fresh weight of the treated plant to that of the untreated plant was calculated with the latter fresh weight taken as 100; and the phytotoxicity and the herbicidal activity were evaluated by the standard given in the table below.
• Cylindrical plastic pots (diameter, 10 cm; height, 10 cm) were filled with upland field soil, and the seeds of barnyardgrass, wild oat, radish and velvetleaf were sowed therein and grown for 10 days in a greenhouse.
• Plastic trays 35 cm x 25 cm x 10 cm were filled with upland field soil, and the seeds of corn, wheat, soybean, sunflower, cocklebur, tall morningglory, hemp sesbania, velvetleaf, redroot pigweed, birdseye speedwell and black nightshade were sowed therein and grown for 3 weeks in a greenhouse. Every two trays were placed in a frame (50 cm x 100 cm x 40 cm) and a given amount of the test compound was sprayed over them by means of a small hand sprayer. The test plants were further grown for 3 weeks in the greenhouse and herbicidal activity and phytotoxicity were examined. The results are shown in Table 3.
• test compound was formulated into an emulsifiable concentrate and applied by diluting it in water (25 liters) with the addition of a spreading agent.
• the plants were generally at the 1 to 4 leaf stage and measured 1.5 to 15 cm in height.
• Cylindrical plastic pots (diameter, 10 cm; height, 10 cm) were filled with upland field soil, and the seeds of barnyardgrass, wild oat, tall morningglory and velvetleaf as well as soybean were sowed therein.
• a given amount of the test compound formulated into an emulsifiable concentrate and dispersed in water was sprayed over the soil by means of a small hand sprayer at a spray volume of 10 liters per are and the soil was mixed well at the depth of 4 cm from the surface.
• the test plants were grown for 20 days in a greenhouse, and herbicidal activity and phytotoxicity were examined. The results are shown in Table 4.
• Plastic trays 35 cm x 25 cm x 15 cm were filled with upland field soil, and the seeds of soybean, cotton, corn, wheat as well as cocklebur, velvetleaf, tall morningglory, prickly sida, pineappleweed and wild buckwheat were sowed therein.
• a given amount of the test compound formulated into an emulsifiable concentrate and dispersed in water was sprayed over the top by means of a small hand sprayer at a spray volume of 10 liters per are. After the spraying, the test plants were grown in a greenhouse for 20 days, and phytotoxicity and herbicidal activity were examined. The results are shown in Table 5.
• W agner's pots (1/5000 are) were filled with paddy field soil and the seeds of barnyardgrass, hardstem bulrush and broad-leaved weeds (e.g. false pimpernel, monochoria, toothcup) were sowed therein at 3 cm depth, and water was poured until the depth of water was 4 cm. Seedlings of rice plants at 3-leaf stage as well as tubers of arrowhead were transplanted therein, and the test plants were grown for 5 days in a greenhouse. At the time of germination, a given amount of the test compound formulated into an emulsifiable concentrate was applied to the pots by perfusion. The test plants were grown for 20 more days, and herbicidal activity and phytotoxicity were examined. The results are shown in Table 6.
• Plastic trays 35 cm x 25 cm x 15 cm were filled with upland field soil, and the seeds of soybean, cocklebur, common ragweed, velvetleaf, prickly sida, sicklepod, tall morningglory, black nightshade, jimsonweed and redroot pigweed were sowed therein.
• a designed amount of the test compound formulated into an emulsifiable concentrate and dispersed in water was sprayed to the soil surface at a spray volume of 10 liters per are. After the spraying, the test plants were grown for 20 days in outdoors (atmospheric temperature: maximum, 30°C; minimum, 12°C; total rainfall: 22 mm), and herbicidal activity and phytotoxicity were examined. The results are shown in Table 7.

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• 1982
  • 1982-11-12 US US06/441,381 patent/US4545812A/en not_active Expired - Fee Related
• 1983
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